Quaternized halomethyl ethers



United States Patent 3,359,131 QUATERNIZED HALOMETHY L ETHERS Robert J.Koshar, Lincoln Township, Washington County,

and Harvey A. Brown, East Oakdale Township, Washington County, Minn.,assignors to Minnesota Mining and Manufacturing Compay, St. Paul, Minn.,a corporation of Delaware No Drawing. Filed May 6, 1960, Ser. No. 27,279Claims. (Cl. 117119.6)

This invention relates to halomethylethers and more particularly tocertain new perfiuoroalkyl-alkylene halomethyl ethers, to the quaternaryammonium salts prepared therefrom, and to a process for renderingtextiles soilresistant as well as oil and water repellent.

The novel halomethylethers of the invention contain a halomethyl groupattached to a perfiuoroalkyl group through an alkyleneoxy radical. Thehalomethylether group is quaternized by reaction with a tertiarynitrogeneous organic base to form a quaternary ammonium salt, sometimeshereinafter referred to as a quaternized halomethyl ether. When theperfluoroalkyl group contains from about 4 to about 12 fully fluorinatedcarbon atoms, it has been found that the novel quaternary ammoniumcompounds of the invention can be employed as textile finishes to treatfibrous materials such as rayon, nylon, wool, silk, polyacrylate andpolyacrylonitrile fibers and the like, and particularly to treatcellulosic materials such as cotton to produce a chemically bonded,soil-resistant, waterand oil-repellent finish thereon without therebyaltering either color or tensile-strength.

While it has heretofore been found possible to produce valuable anduseful soil-resistance, and oiland waterrepellency, in wool and certainsynthetic fibers, it has been difficult to produce lasting effects onthe cellulosic fibers, The finishes heretofore developed for thispurpose, such as those which employ amido-quaternary amines as describedin United States Patent No. 2,303,191, have been relatively easilyremoved, often by a single laundering operation. They have also requiredthe deposit of relatively large amounts of the treating agent on thefibers, as compared with the compositions of the present invention.

It is an object of this invention to provide halomethyl etherspossessing fluorocarbon tails or residues.

Another object of this invention is to provide quaternary ammonium saltspossessing fluorocarbon tails.

Another object of this invention is to provide agents by means of whichfibrous materials can be rendered oiland water-repellent.

Another object of this invention is to provide agents by means of whichcellulosic materials and particularly cotton fibers can be renderedlastingly oiland waterrepellent.

A further object of this invention is to provide oiland water-repellentcellulosic materials such as cotton cloth.

Still another object of the invention is to provide a process forrendering cellulosic materials soil-resistant. Other objects will becomeapparent hereinafter.

In accordance with the above and other objects of this invention certainnovel halomethylethers have been discovered which are useful for theproduction of quaternary ammonium salts containing a perfiuorocarbonmoiety, which may be designated as a fluorocarbon tail or residue. Thesecompounds can be represented by the formula:

R,ROCH X wherein R is a perfiuoroalkyl group containing 4 to 12 carbonatoms, R is a divalent alkylene group selected from the group consistingof CH --CHCl(CH and ( ZLH Patented Dec. 19, 1967 wherein n is an integerfrom 1 to 10, m is an integer from 3 to 12 and X is chlorine or bromine.

The quaternary ammonium salts of the invention which are prepared fromthe above described halomethyl ethers, can be represented by theformula:

wherein R R, and X have the significance set forth hereinabove and Q isthe radical of a tertiary nitrogenous base.

It is important that the perfluorocarbon tail or residue contain atleast four carbon atoms, and the preferred number is six to ten. Aterminal fluorocarbon chain of this minimum length is required in orderto insolubilize and render the end of the molecule both hydrophobic andoleophobic.

The perfiuorocarbon tail structure can include an oxygen atom linkingtogether two perfluorinated carbon atoms, or a nitrogen atom linkingtogether three perfluorinated carbon atoms, since these linkages arevery stable and do not impair the inert and stable fluorocarboncharacteristic of the structure. The R; radical can accordingly be aperfluoroalkyl group, a perfluorocycloalkyl group, or an oxygen-linkedor nitrogen-linked perfluoroalkyl group.

The perfluorocarbon moiety of the molecule is inert and non-polar, andis both hydrophobic and oleophobic. It is repellent not only to oils butalso to hydrocarbons. It imparts unique surface-active andsurface-treating properties not possessed by corresponding compoundshaving a hydrocarbon tail, the latter being oleophilic and highlysoluble in oils and hydrocarbons and lacking the property of impartingsoil-resistance which is a valuable feature of the compounds of thisinvention.

It will be evident that quaternization of the halomethyl ethers of theinvention provides the quaternary ammonium salts of the invention whichmay thus also be referred to hereinafter as quaternizedhalomethylethers.

It has been found that the quaternized halomethyl ethers of theinvention can be applied to woven and nonwoven fabrics, as more fullydescribed hereinafter, to pro vide oiland water-repellency with improvedresistance to laundering and dry cleaning.

The quaternized halomethylethers of the invention may be used as thesole component in the treating vehicle or as a component in a complexmulti-ingredient formulation. For instance, excellent water and oilrepellency and soil resistance is obtained on textile fabrics which aretreated simultaneously with the quaternized halomethyl ethers of theinvention and conventional finishes, such as mildew preventatives, mothresisting agents, crease resistant resins, lubricants, softeners, sizes,flame retardants, anti-static agents, dye fixatives, and waterrepellents. In the treatment of paper the quaternized halomethylethermay be present as an ingredient in a wax, starch, casein, elastomer orwet strength resin formulation.

In addition to oil and water repellency and soil re sistance properties,the quaternized compounds may be used to impart lower surface adhesionvalues and lower coefficient of friction to substrates. Accordingly,they may also be used as mold release agents applied, for example, towooden concrete forms, and related applications.

In the treatment of fabrics and fibrous materials, the quaternizedhalomethyl ethers of the invention may be employed in conjunction withother treating agents, such as crease resisting resins, sizes,softeners, and water repellents, by concurrent or sequential treatments.Known treating agents of these classes are as follows:

Crease resisting resins urea-formaldehyde resins, ethyleneurea-formaldehyde resins, melamine-formaldehyde resins,triazine-formaldehyde resins, epoxy resins, and polyglycol acetals.Sizes starch, casein, glue, polyvinyl alcohol, polyvinyl acetate, methylcellulose, carboxymethyl cellulose. Softenerspolyethylene glycols,polyethylene, dimethyl polysiloxanes, amines and amides derived fromfatty acids and ethylene oxide condensation products of such amines andamides. Water repellents waxes, aluminum salts of fatty acids, siliconeresins,

chromium complexes of fatty acids, N-alkyl amidomethyl pyridinium salts,and melamine-formaldehyde resin condensates with amides from fattyacids.

The compounds of the invention are prepared by reaction of formaldehydeand hydrogen halide, e.g. hydrogen bromide or hydrogen chloride, withthe corresponding fiuorinated alcohol to produce a halomethyl ether,which is not necessarily isolated when quaternization is to be effectedbut is readily quaternized directly by addition of a tertiary amine suchas pyridine. This procedure is conveniently carried out by passing theselected anhydrous hydrogen halide in gaseous form into a solution ofthe alcohol (R ROH) and paraformaldehyde in an inert solvent, such astoluene, benzene and the like until there is substantially no furtherabsorption of the hydrogen halide. As the reaction is not stronglyexothermic, no temperature control is required, although heating fromabout 25 C. to 100 C. (depending to an extent on the boiling point ofthe solvent used) may be resorted to, to insure completion of thereaction.

Another procedure which is very convenient since it avoids the use ofhalide is to react the alcohol and paraformaldehyde with the hydrohalldeof the tertiary nitrogenous base, e.g. pyridine hydrochloride, in asuitable solvent such as the base. Isolation of the quaternary salt isthen carried out as described above adding, if desired, a further amountof an organic solvent such as e.g. ether. The two procedures are to beconsidered equivalent.

The fiuorinated alcohols of the invention are available by the proceduredescribed in copending application Ser. No. 677,229. Aperfluoroalkanesulfonyl chloride containing the desired R radical isadded to a suitable derivative of a terminally unsaturated alcohol suchas the acetate ester, the ester group merely serving as a temporaryprotective expedient for the hydroxyl group, in the presence of a freeradical initiator, to form the correspondingomega-perfluoroalkyl-psi-chloroalkyl ester, which is hydrolyzed toproduce the free alcohol. The latter compound is reduced if the chlorineatom is to be removed to produce the compounds of the invention in whichR is (CH These reactions are represented diagrammatically:

wherein R m and n have the hereinabove set forth significance.

Suitable unsaturated alcohols for use in the process described, whichare converted to their acetates by conventional esterificationprocedures. or may be used directly if desired, are:

allyl alcohol 2-vinyl-ethanol 3-vinyl-propanol 6-vinyl-hexanol9-vinyl-nonanol (i.e. undecenol) 10-vinyl-decan0l 1 l-vinyl-undecanolPerfluoroalkyl alcohols suitable for use in the invention include, forexample, the following:

S-perfiuorobutyl propanol-l 3-perfluorooctyl propanol-l3-perfluorododecyl propanol-l 4-perfluorooctylbutanol-1S-perfluorobutyl-pentanol-1 S-perfluorooctyl pentanol-lS-perfiuorododecyl pentanol-l 8-perfiuorobutyl-octanol-1S-perfluorooctyl-octanol-1 8-perfiuorododecyl-octanol-111-perfluorobutyl-undecanol-l 11-perfiuorooctyl-undecanol-11l-perfluorododecyl-undecanol-l 11- (perfluoro-4-ethylcyclohexyl)undecanol-1 12-perfluorooctyl-dodecanol-l13-perfluorooctyl-tridecanol-1 and the like.

Without isolation of the intermediate halomethylether, quaternization iseffected in the inert solvent employed for the previous reaction afterbrief evaporation to remove excess hydrogen halide, or the reactionmixture may be further exaporated and some other solvent, such asanhydrous ether or dioxane, in which the quaternary salt is insoluble,may be added. The desired tertiary organic base or amine is then addedin the stoichiometric amount while maintaining the reaction mixture at atemperature in the range of about 25 C. to about C. Any tertiarynitrogenous organic base which is capable of forming a salt orquaternary compound is suitable for this purpose, including, forexample, trialkyl amines such as trimethylamine, tributylamine andtriododecylamines; cycloalkyl amines such as tricyclohexylamine; aralkylamines such as benzyl dimethylamine; arylamines such as dimethylaniline;and heterocyclic amines such as pyridine, picoline, lutidine, quinolineand the like. Pyridine is particularly preferred for convenience andeconomy in the formation of cloth-treating agents as shown above.

Illustrative of the quaternized halomethylethers of the invention arethe following:

3-(perfluorobutyl)propanoxymethyl trimethyl ammonium bromide3-(perfluorooctyl)-propanoxymethyl phenyl dimethyl ammonium chloride3-(perfluorododecyl)-propanoxyrnethyl tricyclohexyl ammonium chloride4-(perfluorooctyl)-butanoxymethyl tributyl ammonium bromideS-(perfluorobutyl)-pentanoxyrnethyl pyridinium chlorideS-(perfluorooctyl)-pentanoxymethyl triethyl ammonium bromide5-(perfluorododecyl)-pentanoxymethyl pyridinium chloride8-(perfiuorobutyl)-octanoxymethyl quinolinium chloride8-(perfiuorooctyl)-octanoxymethyl picolinium chloride8-(perfluorododecyl)-octanoxymethyl benzyl dimethyl ammonium chloride1l-(perfluorobutyl)-undecanoxymethyl pyridinium chloride1l-(perfluorooctyl)-undecanoxymethyl pyridinium chloride 11(perfluorododecyl) undecanoxymethyl pyridinium chloride 11-(perfluoro-4-ethyl-cyclohexyl) -undecanoxymethyl trimethyl ammoniumchloride 12-(perfluorooctyl)-dodecanoxymethyl tributyl ammonium chloride13-(perfluorooctyl)-tridecanoxymethyl pyridinium bromide and the like.

The quaternized compounds of the invention are employed for treatingwoven or non-woven fibrous materials including wool, cotton, rayon,actate, nylon and the like textiles, or paper, leather, wood, felt andsimilar organic fibrous constructions, and particularly cellulosicmaterials, by applying the selected quaternary ammonium derivatives, inaqueous medium buffered to about pH 6, to the cloth, removing anyexcess, drying at a temperature in the range of about 40 to 100 C., andheating the dried material to about 100 to 140 C. for a period of theorder of about to 30 minutes to fix the finish. Thereafter the materialis desirably washed in a mildly alkaline aqueous solution to remove anyresidual acidic material, and dried. The treatment may be followed bya'single aqueous wash before drying, if desired, although this may beomitted since subsequent laundering of the treated fabric accomplishesthe same purpose. This treatment may be termed a finishing treatment,since it is most usefully applied after Weaving, forming, dyeing,weighting, filling or the like have been carried out. Cotton cloth sotreated contains residual fluorine, as indicated by standard analyticalmethods, indicating that at least a portion of the treating agent isretained and has probably reacted in some fashion, probably through thehydroxyl groups present in the fiber, although this hypothesis clearlyis not to be construed as limiting the invention.

It is a surprising feature of cotton fabric treated with thesequaternary derivatives that not only is the cloth rendered oilandwater-repellent but also it possesses a a considerable degree of soilresistance, that is, it does not become soiled as readily as untreatedfabric. Furthermore, when soiled the fabrics thus treated are readilylaunderable or dry-cleaned to a clean state, after which they retaintheir oiland water-repellency. The value of cloth so treated, forexample, for childrens clothes, or for uniforms for workers around oilymachinery, automotive service men and the like will be readily apparent.

The color of the fabrics treated with the compositions of the invention,and their tensile strength, are not affected by the treatment. The handof cotton fabrics appears to be improved by the treatment.

It is noted that the finishing treatment of the invention can be appliedto resin-treated, wrinkle-resistant fabrics without adversely affectingthe desirable non-wrinkling feature of such fabrics.

The procedure for the preparation of the quaternized compounds of theinvention, and the application of the latter to fabrics, especiallycellulosic materials are more specifically illustrated in the followingexamples, in which all parts are by weight and all percentages ofsolutions W./V. unless otherwise specified. It will be understood thatthese examples are illustrative only to show the best mode presentlycontemplated of practicing the invention and are not to be construed aslimiting as to the scope of the invention.

Example 1 The following procedure is used to prepareS-perfluorooctyl-pentanol-l.

A mixture of 26.8 g. (0.052 mole) of perfluorooctane sulfonyl chlorideand 5.0 g. (0.050 mole) of 4-pentenoic acid (allyl-acetic acid) isheated for four hours at about 120145 C. in the presence of a catalyticamount 1.0 g.) of di-tertiary butyl peroxide. The reaction mixture isfractionally distilled under reduced pressure and the fraction boilingat about 100 C. at 0.01 mm. is collected. After recrystallization from amixture of chloroform and carbon bisulfide, the4-chloro-5-(perfluorooctyl)-pentanoic acid thus prepared melts at about89-90 C.

The 4-chloro-5-(perfluorooctyl) pentanoic acid thus prepared ishydrogenated by shaking a solution of 8.00 g. (0.0145 mole) of the acidand 2.5 g. (0.062 mole) of sodium hydroxide in a mixture of 30 ml. ofwater and 30 ml. ethanol for 3 hours at 140 C. in a rocking highpressurehydrogenation apparatus, in the presence of 4 g. of Raney nickelcatalyst and with hydrogen supplied at 2500 p.s.i. pressure. Afterremoval of the catalyst and evaporation to dryness, an amorphous residueis obtained comprising sodium 5-(perfluorooctyl)-pentanoate. Bydissolving this residue in water followed by acidification of theresulting solution, the saturated perfluoroalkyl aliphatic acid formedby hydrogenation is recovered as a waxy white solid, which can bedistilled at C. at 0.02 mm. pressure. After recrystallization fromcarbon bisulfide, the S-(perfluorooctyl)-pentanoic acid thus pre' paredmelts at about 86.587.3 C. The procedure described in US. Patent2,666,797, using lithium aluminum hydride, is employed for reduction ofthe acids to the corresponding alcohols. A suspension in ether of 30parts of S-(perfluorooctyl) pentanoic acid is added to a solution of 3parts of lithium aluminum hydride in about 200 parts of anhydrous ether.The reaction mixture is stirred for about 48 hours and then is treatedwith Water and neutralized with sulfuric acid. The reaction mixture isextracted several times with ether, and the ether extracts are combined,dried and fractionally distilled in vacuo. There is obtainedS-(perfluorooctyl)-pentanol boiling at about 108 C. at 2.5 mm. pressureof mercury.

A mixture of 25 parts (0.05 mole) of 5-perfluorooctylpentanol-l and 1.5parts (0.5 mole) of paraformaldehyde in about 85 parts of benzene iswarmed to effect solution and anhydrous hydrogen chloride gas is passedinto the warm solution until there is no further absorption. Thisrequires about 1.5 hours. The solution is evaporated under reducedpressure to remove excess hydrogen chloride and benzene and 3.9 parts(0.05 mole) of anhydrous pyridine is added to the residue. The resultantmixture is warmed whereupon it solidifies with the formation of5-(perfluorooctyl)-pentoxymethyl pyridinium chloride which is suspendedin ether, collected, washed further with ether and dried.

Calculated for N, 2.21%; Found: N, 2.20%.

Example 2 10-chloro-ll-perfluorooctylundecyl acetate is prepared asfollows: A 3-necked flask containing a glass encased magnetic stirringbar and fitted with a thermometer, two addition funnels and water cooledreflux condenser and a subsequent liquid air trap is charged with 30parts of perfluorooctanesulfonyl chloride, 12 parts undecenyl acetateand 2 parts of di-tertiary butyl peroxide. In one addition funnel isplaced 49.5 parts of undecenyl acetate and in the other parts ofperfluorooctanesulfonyl chloride containing a further 2 parts ofdi-tertiary butyl peroxide. The flask is heated to about 120 C. overabout 40 minutes when the reaction commences exothermically and furtheradditions of reactions are made gradually during about a further 30minutes. The reaction mixture is maintained at about C. for about 1 hourlonger during which time 15 parts of sulfur dioxide are collected in theliquid-air-trap. The reaction mixture is distilled under reducedpressure. 1-0-chloro-1l-pe-rfluorooctylundecyl acetate distills at about170 C. at 1.5 mm. Hg as a liquid which solidifies to a white solid atroom temperature.

Reduction of 65 parts of 10-chloro-11-perfiuorooctylundecyl acetate in25 parts of triethylamine with hydrogen at about 2500 p.s.i. and aboutC. for about 2.5

hours in the presence of 3 parts of Raney nickel (previously washed withtriethylamine) provides a solution of 11-perlluorooctyl-undecyl acetatewhich is recovered as an oil by filtration and evaporation.Saponification of the oil in 80 percent aqueous ethanol using potassiumhydroxide in excess provides 1l-perfluorooctylundecanol as a ratherviscous oily liquid boiling at about 120 to 124 C. at about 0.2 mm. Hgwhich solidifies on standing.

The halomethylation procedure of Example 1 is repeated using benzene asa solvent and the intermediate 11- perfluorooctylundecanoxymethylchloride is recovered, taken up in anhydrous ether and reacted withpyridine. 11-perfiuorooctylundecanoxymethyl pyridinium chloride isobtained as white crystals melting at about 78 C. and decomposing atabout 150 C. on further heating.

Calculated: N, 1.95%. Found: N, 1.99%.

The procedure is repeated employing triethylamine in place of pyridineand rather impure ll-perfluorooctylundecanoxym-ethyl triethyl ammoniumchloride is obtained melting from about 85 C. upward and decomposing atabout 120 C.

Calculated: N, 1.90%; C, 42.4%; F, 43.6%. Found: N, 2.04%; C, 42.4%; F,38.1%.

By the same procedure the quinolinium salt is prepared using quinolinein place of pyridine. ll-perfiuorooctylundecanoxy methyl quinoliniumchloride melts at about 120 to 125 C.

Calculated: C, 45.5%; N, 1.83%; F, 42.1%. Found: C, 46.2%; N, 2.08%; F,39.0%.

The procedure is repeated using anhydrous hydrogen bromide in place ofhydrogen chloride to form ll-perfluorooctylundecanoxymethyl bromidewhich is then reacted with pyridine as above. The resultantll-perfiuorooctyl-undecanoxymethyl pyridinium bromide monohydratesoftens at about 90 C. and decomposes above about 175 C.

Calculated (for monohydrate): C, 39.4%; N, 1.84%; Br, 10.5%. Found: C,39.2%; N, 2.3%; Br, 13.7%.

In the same way as described hereinabove for the preparation ofS-perfluorooctyl pentanol, using IO-undecanoic acid in preparation ofthe perfiuoro acid instead of allylacetic acid, there is produced1l-(perfluorooctyl)-undecanoic acid, which on reduction yields11-(perfluorooctyl)- undecanol boiling at about 122-126 C. at 0.10-0.15mm. pressure of mercury and melting at about 69 to 71 C.

A mixture of 40 parts of 1l-perfiuorooctyl-undecanol and 6 parts ofparaformaldehyde in 150 parts of pyridine is refluxed at 100 C. forabout 1 hour and sulfur dioxide is passed into the solution at 90 to 100C. for about /4 hour. The solution is allowed to stand overnight andexcess pyridine is evaporated under reduced pressure. The residue isextracted twice with ether to remove unreacted alcohol. The remainder isdissolved in 100 parts of benzene and the mixture evaporated and driedat 70 C. and 10 mm. Hg pressure for 1.5 hours. The tacky residuecomprising 11-perfiuorooctylundecanoxymethyl pyridinium sulfite isinsoluble in ether or acetone but dissolves in water giving a foamysolution.

Analysis shows the presence of S, 10.3%, and N, 4.8%.

Example 3 By the procedure described above, 64.1 parts ofperfiuoromethanesulfonyl chloride and 81 parts of 10-undecenyl acetateare reacted at 130 to 148 C. for /2 hours in the presence of 4 parts ofbenzoyl peroxide in a pressure vessel and the product,-chloro-1l-perfluoromethyl-undecyl acetate, is isolated by fractionaldistillation as a colorless liquid, boiling from about 120 to 123 C. atabout 0.8 mm. Mg pressure and having n =1.4240.

Calculated for C F H ClO C, 53.2%; F, 180%. Found: C, 53.4%; F, 18.0%.

A mixture of 56.2 parts of 10-chloro-11-perfiuoromethyl undecyl acetateand 3 parts of Raney nickel catalyst (washed with triethylamine) in 50parts of triethylamine is heated at about 145 to 175 C. under about 2000to 2500 p.s.i. of H pressure for 5.5 hours and then cooled and filtered.The solution is evaporated to give a liquid residue. This liquid (48parts) is refluxed for 15 hours with stirring in 100 parts of ethanolcontaining 17 parts of potassium hydroxide in 40 parts of water. Thesaponification mixture is evaporated to remove alcohol, diluted withthrice its volume of water, acidified and thoroughly extracted withether. The ethereal solution is evaporated under reduced pressure toprovide crude 11- perfluoro-rnethyl-undecanol which is convenientlyfreed from unsaturated materials resulting from incomplete reduction bycatalytic hydrogenation.

A total of 48 parts of crude 11-perfiuoromethyl-undecanol containingsome of the corresponding A unsaturated compound is shaken with 5 partsof Raney-nickel catalyst in 51 parts of triethylamine and 35 parts ofethanol at about 150 C. for 2 hours. The filtered reaction mixture isevaporated to dryness and fractionally distilled.11-perfluoromethyl-undecanol boils at about 107 to 109 C. at about 1.5mm. Hg. pressure and melts at about 33 C.

Calculated for C F H O: F, 23.7%; C, 60.0%; Found: F, 22.5%; C, 60.2%.

A mixture of 30 parts of 11-perfiuoromethyl-undecanol and 4 parts ofparaformaldehyde in about parts of toluene is saturated with anhydroushydrogen chloride for about 1 hour until the solution becomes clear. Thetoluene is removed under vacuum (below 1 mm. Hg) at 40 C. The residue istaken up in parts of ether and filtered and 15 parts of pyridine addedto the filtrate. The resultant solution is refluxed for 1 hour and theprecipitate collected. It is11-perfiuoromethyl-undecanoxymethyl-pyridinum chloride melting at about80 C.

Calculated for C F H NOcl- /sH Oz N, 3.75%; F, 15.3%; H O, 1.6%. Found:N, 3.7%; F, 14.0%; H O, 1.4%.

The process for production of soil-resistant, waterand oil-repellentcloth using the quaternary derivatives of the compounds of thisinvention is carried out as follows:

The treating solution is prepared by warming sodium acetate trihydrateand the selected treating agent in water at the desired concentrations,which can range from about 0.1 to about 5 percent, at about 30 to 40 C.until solution is effected. It is to be noted that at higherconcentration the solution tends to become mueilaginous, resembling acolloidal dispersion. The cloth to be treated is soaked in the solutionfor 1 minute, removed and squeezed so that a weight of solutionapproximately equal to 75 to percent of the weight of the cloth isretained. Under these conditions, the preferred concentration oftreating solution ranges from about 0.5 to about 2 percent. The cloth isthen dried for about 10 to 30 minutes at 40 to 100 C. and the treatmentis fixed by heating the cloth for about 5 to 30 minutes at from about100 to C. The fixed, treated cloth is washed for about 30 minutes in anaqueous solution containing 0.1 percent w./v. of sodium lauryl sulfateand 0.2 percent w./v. sodium carbonate, at about 50 to 60 C., rinsedthoroughly and again dried. Other alkaline agents, such as dilute alkalimetal hydroxides, bicarbonates, ammonium hydroxide and the like can beused instead of alkali metal carbonates, to produce a mildly alkalineaqueous washing solution.

The effectiveness of the treatments is determined by means of tests forspray rating, oil repellency rating and visual estimation of soilrepellency both before further treatment and after one or more cycles oflaundering and/ or dry cleaning.

For test purposes, laundering is accomplished by washing in an automaticwashing machine of the stationary tub type using a detergent undernormal household procedures or by means of a standard 60 minute cycle ina Launder-O-Meter, using chip soap as specified in ASTM D-496.Dry-cleaning is performed by available commercial procedures employing,for example, perchloroethylene or naphtha.

Determination of water repellency rating is by means of the Spray Test(Standard Test Method No. 22-52, published in the 1952 Technical Manualand Yearbook of the American Association of Textile Chemists andColorists, vol. XXVIII, p. 136).

Oil repellency of the treated cloth is measured by a severe test inwhich its resistance to penetration by solutions of mineral oil inheptane is determined. (Higher proportions of heptane bring aboutquicker penetration.) A material wet by mineral oil alone in less than 3minutes rates zero, if it is only wet after 3 minutes it rates fifty,while resistance to penetration by a mixture of equal volumes of heptaneand mineral oil rates 100. The ratings for resistance for 3 minutes areas follows:

Percent heptane: Rating 50 20 70 30 80 4O 90 50 100 60 100+ A rating of70 or higher indicates a high degree of resistance to staining by saladoil and the like.

Dry soil resistance simulates soil repellency of a material underespecially exaggerated conditions. A control sample of untreated clothand the treated sample to be tested are shaken together in a paper bagwith about 2 ounces of a standard synthetic soil mixture (having thecomposition described in the report of Salsbury, et 211., AmericanDyestuff Reporter, Mar. 26, 1956, p. 199), then removed and sharplystruck against a solid object to removed loosely adherent soil andcompared visually with a similarly soiled untreated sample. The ratingsare from 0 to 3. These correspond to visual estimation to:

0 as dark as control (untreated cloth sample) 1 slightly less dark thancontrol 2 more than about half as dark as control 3 less than about halfas dark as control While the ratings are to some extent subjective, andmay vary to a certain extent as to the degree of soil involved, it issignificant that there is markedly less soiling of samples treated withthe compounds of the invention and this property is retained afterlaundering.

The synthetic soil mixture is prepared by blending the following:

Parts by wt. Peat moss 38 Portland cement 17.0 Kaolin clay 17.0 Silica(800 mesh) 17.0 Furnace black (high leading, blue tone, powdered,

Malacco) 1.75 Red iron oxide 0.5 Mineral oil (heavy) 8.75

Treating solutions are prepared as described above by warming 1 part ofsodium acetate trihydrate and two parts of each of the followingquaternized compounds of Example 2 in 100 parts of water. These aredesignated by the letters shown.

(A) 11-perfluorooctylhendecaneoxymethyl pyridinum chloride Samples ofcotton jeans cloth are treated with the respective solutions, dried at100 C. for 30 minutes, heated for 5 minutes at 135 C. (A, D and D), or121 C. (B), washed and dried as described above, and rated as follows:

Oil 1 Spray Percent F *Not determined.

All show appreciable soil resistance and retain an appreciablepercentage of oiland water-repellency after laundering or dry-cleaning.Substantially the same results are observed when nylon and woolenfabrics are similarly treated.

The 11-perfluoromethylhendecanoxymethyl pyridinum chloride of Example 3above is applied similarly to cotton cloth and is found to exert noappreciable repellent effect. The perfluoro alkyl group must containmore than one carbon atom and preferably has four or more perfluorinatedcarbon atoms.

The procedure of Example 1 is repeated employing1,1-dihydro-perfluorooctanol and the starting compound is recoveredunchanged; there is no reaction when n of the divalent alkylene group isas low as 1. It is found that n should be from 3 to 12.

3-(perfluoropropyl)-propanol is prepared starting with ethylperfiuorobutyrate as follows: Approximately equimolar quantities ofethyl perfluorobutyrate, methyl acetate and sodium methoxide are used.The ethyl perfluorobutyrate is added to a cooled solution of sodium methoxide in absolute ether, with continued cooling. After stirring thismixture for approximately two hours the methyl acetate is added,whereupon a clear solution forms. The solution is stirred forapproximately 16 hours and then fractionally distilled under reducedpressure, to remove solvents and to obtain methyl3-(prefluoropropyl)-3-keto propionate as the main product. The ketoesterthus obtained is hydrogenated under pressure with Raney nickel catalyst,in ether solution, under the usual conditions, for about two hours. Thecatalyst is removed by filtration and the filtrate is fractionallydistilled in vacuo, whereupon methyl-3-(perfluoropropyl)-3-hydroxypropionate is recovered, boiling at about 85 C. at 15 mm. pressure andhaving refractive index n; =1.3513.

' About 157 parts of the hydroxy ester thus obtained and parts ofphosphorous pentoxide are mixed and allowed to stand for approximately16 hours (a rather mixing). The reaction mixture is then filtered andthe filtrate is purified by fractional distillation. There is obtainedmethyl-3-(perfiuoropropyl) acrylate which boils at 12l124 C. at 732 mm.pressure and has refractive index n =1.3362. The acrylic ester ishydrogenated in ether solution using Raney nickel catalyst and highpressure under the usual conditions. The reaction mixture is filteredand the filtrate is fractionally distilled under reduced pressure. Thereis obtained the corresponding saturated ester, methyl3-(perfluoropropyl)propionate, which boils at 42 C. at 12 mm. pressureand has refractive index n =l.3276. To a solution of 7.6 g. (.2 mole) oflithium aluminum hydride in 500 ml. of ether are added 49 g. (0.191mole) of the methyl-3(heptafluoropropyl)-propionate dissolved in 100 ml.of ether, at such a rate that vigorous refluxing is maintained. Themixture is then stirred for 1 hour and an excess of methanol is added tohydrolyze the complex. The reaction mixture is next acidified withdilute sulfuric acid. The ether layer is separated and the aqueous layeris further extracted with about an equal volume of ether. The combinedether phases are evaporated to remove the ether and the residue isfractionally distilled. The 3-(heptafiuoropropyl)-propanol thus obtainedboils at about 140l41 C. at 745 mm. pressure and has index ofrefraction, 11. =l.3270.

By repeating the procedure of Example 1, employingperfluoro-n-butanesulfonyl chloride,perfluoro-4-ethylcyclohexanesulfonyl chloride, and perfiuorododecanesulfonyl chloride (prepared by the process of Brice et al. as disclosedin US. Patent No. 2,732,398) instead of perfiuorooctanesulfonylchloride, there are obtained, respectively, S-(perfluorobutyl)-pentanoicacid, perfluoro- 4-ethylcyclohexyl pentanoic acid andS-(perfiuorododecyl)-pentanoic acid. Upon reduction, these acids yieldthe corresponding S-(perfiuoropentyl)-pentanol,S-(perfiuoro-4-ethylcyclohexyl)-pentanol andS-(perfluorododecyl)-pentanol, respectively.

When 3 perfiuoropropyl-propanol, perfluorobutylpentanol,5-perfiuoro(4-ethyl cyclohexyl)-pentanol and 5-perfluorododecyl-pentanol are converted to the respective correspondinghalomethyl ethers and quaternized by the procedure of Example 1, usingpyridine, the respective crystalline quaternary chlorides are isolated,viz: 3- (heptafluoropropyl)propanoxymethyl pyridinum chloride,S-nonafluorobutyl)-pentanoxymethyl pyridinium chloride,5-perfluoro(4-ethyl cyclohexyl)pcntanoxymethyl pyridinium chloride andS-perfluorododecyl)-pentonoxymethyl pyridinium chloride. When each ofthese is made up into a treating solution at 2 percent concentrationwith sodium acetate, applied to cotton cloth as described above, andtested for oiland water-repellency, it is found that all except the3-heptafiuoropropylpropanoxymethyl pyridinium chloride providesignificant oiland waterrepellency. The latter compound does not producethis effect, showing that the perfluoroalkyl group must contain 4 ormore carbon atoms.

The solutions used for treating fabrics as set forth above can also beapplied to paper with slight modification in procedure to avoid damagingthe structure of the paper, which, as is well known, is weakened bytreatment with water. Thus, the excess of treating solution is removedby permitting the paper to drip dry or by running the web between rolls,while drying and fixing are accomplished by heating the individualsheets or by hot-roll calendering long strips or continuous rolls. Thetreated paper is oiland water-repellent. Wooden surfaces are renderedoiland water-repellent by applying the solution as a paint, drying andheating as above followed by a mildly alkaline wash and drying again.

Example 5 When the solution designated A in Example 4 above is made upto contain additionally percent of a melamineformaldehyde condensate (ofthe type employed for producing crease resistance) and 1 percent of anaccelerator for the cure thereof and cotton cloth is treated with thissolution and cured following the procedure described above, it is foundthat the washed and dried cloth shows crease-resistance and is oilandwater-repellent. Substantially similar results are obtained when clothinitially treated with a crease-resistance promoting resin issubsequently treated with solution A above.

What is claimed is:

1. A compound of the formula wherein R; is perfluoroalkyl having 4 to 12carbon atoms, Q is a tertiary nitrogenous organic residue selected fromthe group consisting of trialkylamino having 3 to about 36 carbon atoms,tricyclohexylamino, aralkyl amino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidino andquinolino, X is a halogen of the group consisting of chlorine and 12bromine and R is a divalent radical selected from the group consistingof:

CH CHCl(CH and wherein n is an integer from 1 to 10 and m is an integerfrom 3 to 12.

2. A compound of the formula:

wherein R is perfluoroalkyl of 4 to 10 carbon atoms,

Q is a tertiary nitrogenous organic residue selected from the groupconsisting of pyridino, picolino, lutidino, quinolino anddimethylanilino, X is a halogen selected from the group consisting ofchlorine and bromine and R is a divalent radical selected from the groupconsisting of:

CH -CHCl-(CH and wherein n is an integer from 1 to 7 and m is an integerfrom 3 to 9.

4. A compound of the formula R ROCH X wherein R is perfluoroalkyl of 4to 10 carbon atoms, X is halogen selected from the group consisting ofchlorine and bromine, and R is a divalent radical selected from thegroup consisting of:

wherein n is an integer from 1 to 7 and m is an integer from 3 to 9.

5. 5-perfluorooctylpentyloxymethyl pyridinium chloride.

6. Omega-perfiuorooctyl-undecanoxymethyl pyridinium chloride.

7. A compound of the formula R; (CH ocn x wherein R is perfluoroalkylhaving 4 to 12 carbon atoms, X is halogen of the group consisting ofchlorine and bromine and m is an integer from 3 to 12.

8. The process for rendering fibrous materials waterand oil-repellent,which comprises treating the fibrous material with a compound of theformula:

wherein R, is perfluoroalkyl having 4 to 12 carbon atoms, Q is atertiary nitrogenous organic residue selected from the group consistingof trialkylamino having 3 to about 36 carbon atoms, tricyclohexylamino,aralkyl amino having about 8 carbon atoms, aryl amino having about 8carbon atoms, pyridino, picolino, lutidino and quinolino, X is a halogenof the group consisting of chlorine and bromine and R is a divalentradical selected from the group consisting of:

-CH CHCl-(CH and wherein n is an integer from 1 to 10 and m is aninteger from 3 to 12; in aqueous medium buffered to about pH 5.5 to 6.5,drying the treated fibrous material and heating the dried, treatedmaterial to a temperature in the range of about 100 to 140 C. for aperiod of about to 30 minutes.

9. A fabric finished with a compound of the formula:

--CH CHCl CH and CH2 m wherein n is an integer from 1 to and m is aninteger from 3 to 12, whereby the fabric contains residual combinedfluorine and has oiland Water-repellent properties.

10. A cellulosic fabric having oiland water-repellent properties,finished with 11-perfiuorooctane-hendecanoxymethyl pyridiniu m chloride.

References Cited UNITED STATES PATENTS 2,727,923 12/1955 Husted 260567.62,767,189 10/1956 Erickson 260-5676 2,804,402 8/1957 Williams 117-139.42,812,350 11/1957 Niederhauser 260567.6 2,913,500 11/1959 Becke et al.260614 2,915,524 12/1959 Truitt 260-297 OTHER REFERENCES Knunyants etal.: Chem. Abstracts, vol. 43, col. 6163 (1949).

Brey et al.: J. Am. Chem. Soc., vol. 79, pp. 6533-6 (1957).

Park et al.: Chem. Abstracts, vol. 53, col. 6058 (1959).

Jarvis et al.: J. Phys. Chem., vol. 63, pp. 727-734 (1959).

JOHN D. RANDOLPH, Primary Examiner.

D. T. MCCUTCHEN, I. MARCUS, Examiners.

R. T. BOND, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,359;131 December 19, 1967 Robert J. Koshar et 211.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

} Column 5, line 11, for "actate" read acetate column 10, lines 57 and58, for "(a rather mixing)" read M (a rather strong exothermic reactionbeing noted shortly after mixlng) column 11, line 27, for"5-nonaf1uorobuty1)-" read 5-(nonafluorobuty1)- Signed and sealed this14th day of January 1969.

(SEAL) Attest:

EDWARD J. BRENNER Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

1. A COMPOUND OF THE FORMULA
 8. THE PROCESS FOR RENDERING FIBROUSMATERIALS WATERAND OIL-REPELLENT, WHICH COMPRISES TREATING THE FIBROUSMATERIAL WITH AA COMPOUND OF THE FORMULA: